Evaluation of the rate of abiotic and biotic degradation of oxo-degradable polyethylene

The recent introduction of oxo-degradable additive in the Argentinean market has motivated the study of the effect of abiotic (temperature and ultraviolet (UV) radiation) and biotic (aerobic in compost) degradation on the structure and mechanical behavior of films of polyethylene (PE) and oxo-degradable polyethylene (PE+AD).Physico-chemical tests show that the failure strain and the carbonyl index of degraded PE and PE+AD samples depend on the UV irradiation dose. Furthermore, the additive plays a crucial role in the degradation and subsequent decay of the molecular weight.It was observed that, for the same dose, the most deteriorated material was the one exposed to the lowest irradiance, emphasizing the importance of the time of exposure to UV radiation. The ratio between the irradiance and the critical dose, is a characteristic time associated to the sharp decay on the failure strain. The critical dose decreases significantly when increasing the temperature of the photo-degradation assay.PE is more susceptible to thermal degradation than PE+AD; the latter only degrades under thermal aging at the highest temperature.Initially biotic degradation in compost showed an increasing production of carbon dioxide for both previously UV-degraded and untreated PE+AD. It is also remarkable that UV-degraded samples of PE and PE+AD with differences in their abiotic degradation level, reached the same final biotic degradation level. It was observed that although the additive increased the abiotic photodegradation, the molecular weight reduction in compost was not enough to reach the maximum biotic degradation level established by international standards for biodegradable materials.     

Studies on the photo-oxidative degradation of LDPE films in the presence of oxidised polyethylene

This paper reports the results of photo-oxidative degradation studies of LDPE in the presence of varying amounts of oxidised polyethylene (OPE), which was prepared by heating LDPE films containing 0.1% cobalt stearate in oxygen atmosphere at 100 °C. OPE, with a CI of 12 was used as an additive for LDPE. Varying amounts of OPE (0.5-5%) were blended with polyethylene in an extruder and films of 70 μm thickness were prepared by film blowing process. The physico-chemical properties of the films were evaluated and these were found to be proportional to the amount of OPE. The films thus obtained were subjected to UV-B exposure at 30 °C for extended time periods. The chemical and physical changes induced by UV exposure were followed by monitoring the changes in mechanical properties (tensile strength and elongation at break), carbonyl index (CI), morphology, molecular weight, MFI and DSC crystallinity. Incorporation of OPE was found to be effective in initiating the photo-degradation of LDPE in relatively short span of time and the degradation was found to be proportional to the amount of OPE in the formulation.     

Surface changes brought about by corona discharge treatment of polyethylene film and the effect on subsequent microbial colonisation

Microbial colonisation of synthetic plastic films is normally slow, which affects the total period of biodegradation. Correlation between the modified surface condition and the ability for microorganisms to colonise low-density polyethylene (LDPE) film was studied. Corona discharge treatment was applied to obtain enriched and activated surface condition of LDPE film. It was found from water contact angle and FTIR spectrum evaluations that surface energy was significantly increased due to production of free radicals. Stabilised oxidised LDPE surface was also obtained by further exposure to the corona which gave more suitable condition for subsequent colonisation. Results were compared with UV irradiated (photo-oxidised) LDPE films. Colonisation of corona discharged and UV treated LDPE films were tested in the laboratory environment using known fungal isolates and in a natural compost environment. More active microbial colonisation was observed in all cases for corona discharged and UV treated LDPE films. Far longer UV exposure was required to have the same physicochemical and biological effect as the corona discharge treatment.     

含羧酸共生稀土光敏剂的低密度聚乙烯膜紫外光氧化降解

含羧酸共生稀土光敏剂的低密度聚乙烯膜紫外光氧化降解林宜超（福建省测试技术研究所福州３５０００３）近年来，许多作者先后研究并开发出含硬脂酸铈（ＣｅＳｔ３）光敏剂的可控光降解低密度聚乙烯（ＬＤＰＥ）［１，２］、高密度聚乙烯［３］、聚丙烯［４］、聚苯乙烯...     

Oxidation and biodegradation of polyethylene films containing pro-oxidant additives: Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation

Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation on the oxidation and biodegradation of linear low density poly(ethylene) PE-LLD films containing pro-oxidant were examined. To achieve oxidation and degradation, films were first exposed to the sunlight for 93 days during the summer months followed by their incubation with fungal strains previously isolated from the soil based on the ability to grow on the oxidized PE-LLD as a sole carbon source. Some films were also thermally aged at temperatures ranging between 45°C and 65 °C, either before or after fungal degradation. Films with pro-oxidant additives exhibited a higher level of oxidation as revealed by increase in their carbonyl index (COi). In addition to increase in the COi, films showed a slight increase in crystallinity and melting temperature (T_m), considerably lower onset degradation temperatures, and a concomitant increase in the % weight of the residues. The level of oxidation observed in thermally aged films was directly proportional to the aging temperature. The PE-LLD films with pro-oxidant exposed to sunlight followed by thermal aging showed even higher rate and extent of oxidation when subsequently subjected to fungal biodegradation. The higher oxidation rate also correlated well with the CO₂ production in the fungal biodegradation tests. Similar films oxidized and aged but not exposed to fungal biodegradation showed much less degradation. Microscopic examination showed a profuse growth and colonization of fungal mycelia on the oxidized films by one strain, while another spore-producing strain grew around the film edges. Data presented here suggest that abiotic oxidation of polymer's carbon backbone produced metabolites which supported metabolic activities in fungal cells leading to further biotically-mediated polymer degradation. Thus, a combined impact of abiotic and biotic factors promoted the oxidation/biodegradation of PE-LLD films containing pro-oxidants.     

Degradation products formed during UV exposure of polyethylene-ZnO nano-composites

Photodegradation of low density polyethylene (LDPE) containing nano-particulate ZnO has been studied using FTIR to follow the development of oxidation products in the polymer film and to monitor carbon dioxide evolved as a principal product of oxidation. The degradation behaviour of ZnO-free LDPE has been compared with that of compounds containing 0.25% and 0.75% ZnO and these results are compared with those obtained using similar films containing nano-particulate TiO₂. Under UV exposure, the presence of ZnO accelerated the development of carbonyl groups and CO₂ production. The carbonyl group development was more rapid when TiO₂ was used whereas ZnO caused greater CO₂ generation. Carbonyl group development seemed to correlate better with the reduction in mechanical properties whereas CO₂ generation correlated better with weight change measurements. The influence of ZnO on the oxidation pathways in LDPE is discussed; it is proposed that photo-oxidation is relatively much more likely to occur at terminal sites (rather than at pendent sites) when ZnO is present.     

High photocatalytic degradation activity of polyethylene containing polyacrylamide grafted TiO2

A novel photocatalytic polyacrylamide grafted TiO₂ (PAM-g-TiO₂) nanocomposite was prepared and embedded into a low density polyethylene (LDPE) plastic. Photocatalytic degradation of the LDPE/PAM-g-TiO₂ composite film was carried out under ambient conditions under ultraviolet light irradiation. The properties of composite film were compared with those of the pure LDPE film by measuring the changes in weight loss, carbonyl index, molecular weight, tensile strength and elongation at break. PAM-g-TiO₂ embedded LDPE showed highly enhanced photocatalytic degradation. Irradiating the LDPE/PAM-g-TiO₂ composite film for 520 h under UV light reduced its weight by 39.85% and average molecular weight (M_w) by 94.60%, while that of pure LDPE film was only 1.03% and 69.59%, respectively. The addition of PAM-g-TiO₂ brought about the good dispersion of TiO₂ in LDPE matrix and improved the hydrophilicity of composite film, which were able to facilitate the degradation of LDPE. The photocatalytic degradation mechanism of the films is briefly discussed.     

Determination of radiolysis products in gamma-irradiated multilayer barrier food packaging films containing a middle layer of recycled LDPE

Volatile and non-volatile radiolysis products and sensory changes of five-layer food packaging films have been determined after gamma irradiation (5–60 kGy). Barrier films were based on polyamide (PA) and low-density polyethylene (LDPE). Each film contained a middle buried layer of recycled LDPE or 100% virgin LDPE (control samples). Data showed that a large number of radiolysis products were produced such as hydrocarbons, alcohols, carbonyl compounds, carboxylic acid. These compounds were detected in the food simulant after contact with all films even at the lower absorbed doses of 5 and 10 kGy. The type and concentration of radiolysis products increased progressively with radiation dose, while no new compounds were detected as a result of the presence of recycled LDPE. In addition, irradiation dose appears to influence the sensory properties of table water in contact with films.     

Effect of cobalt carboxylates on the photo-oxidative degradation of low-density polyethylene. Part-I

The effect of three cobalt carboxylates of increasing chain length, namely cobalt laurate, cobalt palmitate and cobalt stearate on the photo-oxidative degradation of low-density polyethylene (LDPE) films has been investigated. LDPE films containing cobalt carboxylates were irradiated with UV-B light at 30 °C for extended time periods. FTIR spectroscopy, mechanical testing, morphological studies, molecular weight, density and MFI measurements were performed to monitor the degradation behaviour. The results of these studies were analysed to explain the structural and chemical modifications taking place in the polyethylene matrix due to UV-B exposure. FTIR studies indicate that the degradation is dominated by formation of carbonyl and vinyl species. The studies on mechanical properties reveal that samples containing cobalt carboxylates, become mechanically fragile after UV exposure for 400 h, while neat LDPE exhibits insignificant changes during this period. The degradation was found to increase proportionally with increasing chain length and follows the order CoSt₃ > CoPal₃ > CoLau₃. Migration studies were performed on food simulant systems to investigate the applicability of these films for food packaging.     

Effect of benzil and cobalt stearate on the aging of low-density polyethylene films

We report an investigation of the effect of benzil and cobalt stearate on the degradation behaviour of LDPE films. Thin films (70 μ) containing these additives were prepared by sheeting process. The effect of heating, exposure to UV-B and natural weathering of LDPE films in the presence/absence of additives was investigated. Changes in the tensile properties, carbonyl index and density were used to investigate the degradation behaviour. Attempts have been made to correlate the results as a function of mixed additives. In contrast to the activity of typical triplet activators, benzil was found to be incapable of initiating thermal- or photo-degradation of LDPE films. However, an accelerated rate of oxidation was observed, primarily due to cobalt stearate, in the case of compositions containing a combination of benzil and cobalt stearate. All samples were found to be more susceptible to thermo-oxidation than to UV or natural weathering.     

光降解性聚乙烯薄膜降解过程的表征

用全反射傅里叶红外光谱、Ｘ射线光电子能谱和示差扫描量热仪研究了含光敏剂的低密度聚乙烯薄膜在光降解过程中降解速率的变化规律，结果表明，光降解性聚乙烯薄膜在降解过程初期，降解速率很小，光敏剂显示抗氧化剂性能；降解２４ｈ后，降解速率迅速增加，直至薄膜破坏，光敏剂显示光引发剂性能。作为对比，同时研究了光敏剂和其它两种添加剂对聚乙薄膜光解速率的协同效应和两种添加剂体系显示的性能。     

Abiotic and biotic degradation of oxo-biodegradable polyethylenes

Conventional polymeric materials accumulate in the environment due to their low biodegradability. However, an increase in the biodegradation rate of these polymers may be obtained with the addition of pro-degrading substances. This study aimed to evaluate abiotic and biotic degradation of polyethylenes (PEs) using plastic bags of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) formulated with pro-oxidant additives as test materials. These packaging materials were exposed to natural weathering and periodically analyzed with respect to changes in mechanical and structural properties. After a year of exposure, residue samples of the bags were incubated in substrates (compost of urban solid waste, perlite and soil) at 58 °C and at 50% humidity. The biodegradation of the materials was estimated by their mineralization to CO₂. The molar mass of the pro-oxidant-activated PE decreased and oxygen incorporation into the chains increased significantly during natural weathering. These samples showed a mineralization level of 12.4% after three months of incubation with compost. Higher extents of mineralization were obtained for saturated humidity than for natural humidity. The growth of fungi of the genera Aspergillus and Penicillium was observed on PE films containing pro-oxidant additives exposed to natural weathering for one year or longer. Conventional PE films exposed to natural weathering showed small biodegradation.     

Degradation of abiotically aged LDPE films containing pro-oxidant by bacterial consortium

The degradation of abiotically aged low density polyethylene (LDPE) films containing trace quantities of a representative pro-oxidant (cobalt stearate) was investigated in the presence of well defined enriched microbial strains namely, Bacillus pumilus, Bacillus halodenitrificans and Bacillus cereus in Basal salt medium. The films were initially subjected to an abiotic treatment comprising UV-B irradiation, and subsequently inoculated with the bacterial strains. The degradation in the polymeric chain was monitored by changes in the mechanical, morphological, structural and thermal properties. The abiotic treatment led to the formation of extractable oxygenated compounds as well as unoxidised low molecular weight hydrocarbons, which was confirmed by GC-MS studies. These were utilized by the bacterial consortium in the subsequent biotic phase and led to a mass loss of the polymer (8.4 ± 1.37%), which was also accompanied by an increase in the bacterial count. A decrease in the surface tension of the cell free medium was observed, which indicates that the bacterial consortium produced extracellular surface active molecules in order to enhance the bioavailability of the polymeric fixed carbon. The spectroscopic investigations reveal that the bacteria preferentially consume the oxygenated products leading to a decrease in the Carbonyl Index (CI), which in turn leads to an increase in the initial decomposition temperature as observed in the TGA traces. The morphological investigations reveal a biofilm formation on the surface, which was found to be scattered in certain regions and not uniform on the polymeric surface.     

高性能光催化降解聚乙烯薄膜的研究

利用酸性蓝BGA染料敏化的纳米TiO2作为光催化剂, 与低密度聚乙烯(LDPE)树脂复合制备了具有可见光催化降解性能的复合塑料薄膜. 采用SEM、FTIR、VHX-100数码显微镜和高温凝胶渗透色谱(HTGPC)等分析技术系统地研究了该塑料薄膜在紫外光和太阳光照射下的降解性能. 探讨了塑料薄膜在光辐照前后的力学性能、质量和分子量变化规律. 研究结果表明, 该薄膜在经紫外线照射5 d后质量损失达到17.6％, 数均分子量由21800降低为5900; 经太阳光照射48 d后质量损失达到12.5％, 分子量降为8100. 辐照后薄膜拉伸强度和断裂伸长率显著降低, 羰基含量升高.     

Identification of carbonyl species of weathered LDPE films by curve fitting and derivative analysis of IR spectra

We describe the examination of the weathering degradation of LDPE (low density polyethylene - locally produced B24/2 and imported LDPE 2100T), supplied by two different manufacturers and processed into films for greenhouse coverings, over several months in a sub-Saharan region of Algeria. The three IR regions most affected by weathering degradation are 800–1100 cm⁻¹, 1680–1800 cm⁻¹ and 3300–3600 cm⁻¹. The IR spectral region most affected by the aging process is the carbonyl region. Curve fitting combined with derivative spectroscopy revealed that the composite carbonyl band encompasses more than 10 different oxidation products. The most significant among these in terms of absorbance are carboxylic acids, ketones, aldehydes and esters. The oxidation kinetics with respect to the type of LDPE film shows that B24/2 LDPE undergoes less oxidization than LDPE 2100 T. Calculating the concentrations of different carbonyl species compared to their respective absorbances indicates that the aldehydes are the predominant component of the final compound, rather than the carboxylic acids.     

Influence of metal ion on the degradation of LDPE at the composting temperatures

Low Density Polyethylene(LDPE) films with additives that contain metal ions were subjected to accelerated degradation at simulated composting temperatures. The mechanical properties and viscosity-average molecular weight of the samples, during the degradation, were determined and the degradation mechanism was studied. The results show that the samples containing metal ion show considerable decreases. Percentage crystallinity of LDPE in the samples has changed obviously during the degradation. [POOH] increases during the early stage of degradation followed by a more or less flat maximum before it starts to decrease, but carbonyl index shows a polynomial increase during the degradation.     

Self‐initiating performance of maleic anhydride on surface photografting polymerization

Maleic anhydride (MAH) was photografted onto low‐density polyethylene (LDPE) films with a grafting efficiency of about 70% in the absence of a photoinitiator. The self‐initiating performance was attributed to a mechanism of abstracting hydrogen atoms from LDPE chains by excited MAH dimers. The supporting experimental results were as follows: (1) the far‐UV radiation (200–300 nm) was indispensable for the graft polymerization and 2) the crosslinking reaction of LDPE inevitably accompanied the grafting of MAH. In addition, the initiation performance of MAH was further confirmed by surface photografting of acrylic acid in the presence of MAH, where MAH was used as the photoinitiator. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3246–3249, 2001     

LDPE Transformation by Exposure to Sequential Low-Pressure Plasma and TiO2/UV Photocatalysis

Low-density polyethylene (LDPE) sheets (3.0 ± 0.1 cm) received sequential treatment, first by the action of direct-current low-pressure plasma (DC-LPP) with a 100% oxygen partial pressure, 3.0 × 10⁻² mbar pressure, 600 V DC tension, 5.6 cm distance, 6-min treatment. Then, sheets were submitted to TiO₂ photocatalysis at UV radiation at 254 nm (TiO₂/UV) with a pH value of 4.5 ± 0.2 and a TiO₂ concentration of 1 gL⁻¹. We achieved a complementary effect on the transformation of LDPE films. With the first treatment, ablation was generated, which increased hydrophilicity. With the second treatment, the cavities appeared. The changes in the LDPE sheets’ hydrophobicity were measured using the static contact angle (SCA) technique. The photocatalytic degradation curve at 400 h revealed that the DC-LPP photocatalysis sequential process decreased SCA by 82°. This was achieved by the incorporation of polar groups, which increased hydrophilicity, roughness, and rigidity by 12 and 38%, respectively. These sequential processes could be employed for LDPE and other material biodegradation pretreatment.     

Multi-component analysis of low-density polyethylene oxidative degradation

The oxidative degradation of polyethylene in various conditions has been studied. In order to gain insight into the oxidation process, a method for the curve-fitting analysis of the IR carbonyl band between 1800 cm⁻¹ and 1600 cm⁻¹ in oxidized low-density polyethylene (LDPE) has been developed. Up to 10 components were needed to fit the band envelope, whose assignments and peak positions were based on the literature and on the synthesis of an appropriate model compound. The determination of the other band parameters, such as peak width and peak shape, necessary for reliable best fitting of the absorbance envelopes, was obtained by overall fitting optimization process. By using the available extinction coefficients, the quantitative determinations of the main oxidized species, i.e. ketones, carboxylic acids, esters, γ-lactones and ketoacids, were obtained with a reasonable confidence by rigorous parameter setting. The method was applied to the IR analysis of LDPE samples oxidized in different conditions (under thermal and irradiation stimulation), either as beads or films, as a function of time. Total hydroperoxide concentrations were also quantitatively estimated by a modified iodometric titration procedure. A good linear correlation between concentrations estimated by chemical titration and by intensity analysis of the free hydroperoxide IR band was observed.